Process for the preparation of novel dihydroxy-1,4-dioxanes

ABSTRACT

1. A DIHYDROXY-1,4-DIOXANE COMPOUND REPRESENTED BY THE FOLLOWING FORMULA:   A&lt;(-O-CH(-OH)-CH(-OH)-O-)   WHEREIN A REPRESENTS   -CH(-R1)-CH(-R2)- OR Z&lt;(-CH(-)-CH(-)-)   AND WHEREIN R1 REPRESENTS HYDROGEN, ALKYL OF FROM 1 TO 18 CARBON ATOMS, MONOHALOALKYL OF FROM 1 TO 8 CARBON ATOMS, ALKOXYALKYL HAVING A TOTAL NUMBER OF FROM 2 TO 13 CARBON ATOMS, PHENYL OR PHENOXYALKYL HAVING A TOTAL NUMBER OF FROM 7 TO 18 CARBON ATOMS; R2 REPRESENTS ALKYL OF FROM 1 TO 18 CARBON ATOMS, MONOHALOALKYL OF FROM 1 TO 8 CARBON ATOMS, ALKOXYALKYL HAVING A TOTAL NUMBER OF FROM 2 TO 13 CARBON ATOMS, PHENYL OR PHENOXYALKYL HAVING A TOTAL NUMBER OF FROM 7 TO 18 CARBON ATOMS; AND Z REPRESENTS CARBON-TO-CARBON CHAIN OF 4 CARBON ATOMS TO FORM A NON-SUBSTITUTED OR MONO-SUBSTITUTED AROMATIC CARBON RING OF 6 CARBON ATOMS, THE SUBSTITUENT ON SAID RING BEING ALKYL OF FROM 1 TO 5 CARBON ATOMS.

United States Patent Office 3,847,948 P e t d Nov. 12, 1974 3,847,948 PROCESS FOR THE PREPARATION OF NOVEL DIHYDROXY-1,4-DIOXANES Nobuo Yamamoto, Minami-Ashigara-machi, Japan, assiguor to Fuji Photo Film Co., Ltd., Kanagawa, Japan No Drawing. Continuation-impart of abandoned application Ser. No. 850,673, Aug. 15, 1968. This application June 4, 1971, Ser. No. 150,164

Claims priority, application Japan, Aug. 17, 1968, 43/ 58,799 Int. Cl. C07d 15/12, 15/18 U.S. Cl. 260340.3 15 Claims ABSTRACT OF THE DISCLOSURE Dihydroxy-1,4-dioxane derivatives represented by the following formula wherein A represents wherein A is the same as defined above, with glyoxal and recovering the dihydroxy-1,4-dioxane derivative, is disclosed.

CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of U.S. application Ser. No. 850,673, filed Aug. 15, 1968, entitled Process for Hardening Gelatin, now abandoned.

BACKGROUND OF THE INVENTION Field of the Invention This invention relates to novel dihydroxy-1,4-dioxane derivatives and a process for preparing the same.

Description of the Prior Art The dihydroxy-l,4-dioxane derivatives represented by the above formula have not been known heretofore. These compounds possess interesting properties with respect to the chemical modifying of high-molecular-weight substances having active groups such as amino and hydroxyl groups.

Heretofore, 2,3-dihydroXy-l,4-dioxane corresponding to the above formula when both R and R represents a hydrogen atom, has been known as a gelatin-hardener for use in the production of photographic sensitive materials (see, e.g., U.S. Pat. No. 2,870,013), but has been found unsatisfactory for a number of reasons. 2,3-dihydroxy- 1,4-dioxane, depending upon some photographic emulsions, adversely affects the characteristics of photographic sensitive materials, causing such disadyantages as an increase in fog of the photographic emulsions, a decrease in sensitivity and the occurrence of -posthardening due to its slow hardening reaction with the gelatin contained in the photograph sensitive material. Difficulties are encountered in attempting to improve the mechanical strength, such as the resistance to abrasion of a gelatin-containing layer of the photographic sensitive material, although the compound could increase its resistance to water. r, I

In addition, British Pat. No.. 926,313 discloses a method of hardening gelatin by incorporating therein an addition compound obtained by reacting at least 2 moles of glyoxal with one moleof a saturated or unsaturated aliphatic compound having in its molecule an --OH group separated by a chain of at least two carbon atoms from either another OH group or an NHg or -NH group The present inventors extensive work has led to a successful synthesis of novel dihydroxyQlA-dioxane derivatives expressed by the above formula, and it has been found that when used as hardener's for photographic sensitive materials, these compounds 'sufier far less from the above-mentioned defects than the known compound 2,3-dihydroxy-1,4-dioxane.

Accordingly, a principal object of this invention is to provide novel dihydroxy-lA-dioxane derivatives expressed by the above formula and a process for producing the same.

Additional objects and advantages will become apparent from the following description.

SUMMARY OF THE INVENTION The present invention provides novel dihydroxy-1,4-dioxane compounds of the formula:

wherein A represents .o m c/ 1. s L R:

where R represents a hydrogen atom, an alkyl group, a

\ haloalkyl group, a haloalkyl group, an alkoxyalkyl group, an aryl group or an aryloxyalkyl group; R represents Ho-A-oH wherein A has the same meaning? as above defined, with glyoxal.

Specific compound are-described in the following description.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the compofihds of the present invention are as follows:

Compound (1) CH-OH lmo i oneon I I I on CH-QH qfisi dro O. i r I Compound (7)v I i H20 Nun-on on EOE-H lCompound (8) Iii: I

attired- 9);

tannins;

I" .i; 1 Eompound (11) i i f on-0H i on Cl1-OH Compound (12) O ,r V CH-OHE CH -iOH t 0 Compound (13) 0\ CH3 CHI-0H CH-OH CH3 It is to be understood that the above compounds are only examples of the compounds of the present invention, and one of ordinary skill in the art should be able to formulate additional compounds not specifically men tioned but within the description in this application.

More specifically defining R and R the alkyl, alkoxy: alkyl and haloalkyl groups may each contain from 1 to about 18 carbon atoms; the aryl group includes groups such as phenyl and the like; and the term aryloxyalkyl iii'cludes groups such as phenoxy-alkyl having from about 7 'to about 18 carbon atoms.

The unsaturated carbon ring attached to the oxygencontaining ring, i.e., the ring including Z, may contain from about 4 to about 8 carbon atoms wherein the substituents on the unsaturated ring may be alkyl groups having from 1 to about 5 carbon atoms.

Other groups not specifically enumerated above but included within the terms alkyl, haloalkyl, alkoxya'lkyl, aryl and aryloxyalkyl are deemed to be within the scope of the present invention.

The process of the present invention generally comprises reacting a dihydroxy compound with glyoxal.

Stated more specifically, the dihydroxy 1,4 dioxane compounds of the present invention are prepared either by mixing the above-identified dihydroxy compound with an aqueous solution of glyoxal and allowing the mixture to stand at room temperature, or by reacting the dihydroxy compound with an aqueous solution of glyoxal on a desiccant such as phosphorus pentoxide or an alkali metal hydroxide at normal atmospheric pressure or at 1 reduced pressure. The desiccant is not a reactant and does not add to the reaction mixture, and hence, any suitable desiccant can be employed, with a person or ordinary skill in the art being able to select appropriate desiccants by either trial and error or some other minimum amount of experimentation.

Typical examples of the dihydroxy compound which,

may be employed in the present process include the following: 3 -chloro-1,2-propanediol, 1,2-0ctadecanediol, 1,2-

propanediol, 2,3-butanediol, 2,3-pentanediol, 1,2-octanediol, 1,2-dodecanediol, 3-n-butoxy-1, 2-propanediol, 3-ndodecyloxy- 1,2 propanediol, 2-phenyl-1,2-ethanediol, 3- phenoxy-1,2-propanediol, catechol, and 4-tert.-butyl catechol. r I

From 0.8 to 1.2 moles of the dihydroxy compound are reacted with each mole of glyoxal to produce the compounds of the present invention, with a 1/ 1 molar ratio being preferred.

The reduced pressure may vary as desired and need not be limited to a specific range; however, a reduced pressure of from about 500 to about 0.01 mm. Hg is satisfactory with from about 300 to about 0.01 mm. Hg being preferred.

.The terminology room temperature generally includes temperatures of from about 10 to about 40 C.

The reaction time is not to be limited, but it is gener--- ally that time necessary to substantially complete .solidification oi the mixture. It will be understood by those skilled inthe art that-the time may vary depending on the reactivity of the reactants, the properties of the desiccant employed and the reaction pressure, etc. Generally,

however, the reaction time varies from about 1 to about 20 days.

The preparation of the compounds of the present in- EXAMPLE 1 Preparation of compound (2) A mixture of 55.3 grams of 3-chloro-l,2-propanediol and 72 grams of a 40% aqueous solution of glyoxal was maintained under vacuum on phosphorus pentoxide until it was almost solidified. With the addition of a small amount of acetone, the resulting solidified mixture was filtered to yield 90 grams of a white crystal. Recrystallization of this crude crystal from 120 ml. of acetone produced 72 grams of compound (2) in a pure form. The product was found to have a melting point of 97-99" C. The elemental analysis of the product revealed the following result. 7

Calculated for C H ClO C, 35.61%; H, 5.34%. Found: C, 35.76%; H, 5.47%.

The foregoing procedure will be referred to as procedure A (i.e., the use of a desiccant).

EXAMPLE 2 Preparation of compound (7) 14.3 grams of 1,2-octadecanediol, which by nature is difiiculty soluble in water, was dissolved into 80 ml. of dioxane, and 7.7 grams of a 38% aqueous solution of glyoxal was added. The resulting mixture was allowed to stand for two days at room temperature. The precipitated white crystal was recovered by filtration, and recrystallized twice from acetone thereby to yield 9.5 grams of compound (7) which was found to have a melting point of 90-905 C. The elemental analysis of the product revealed the following result:

Calculated for C H O C, 69.77; H, 11.63%. Found: C, 69.99%; H, 11.97%.

The foregoing procedure will be referred to as procedure -B.

EXAMPLE 3 Preparation of compounds (1), (3)(6) and (8)-(13) Each of these compounds was prepared by procedure A or procedure B, described in Example 1 or Example 2 respectively. The hydroxy compounds used, the operational procedures employed and the physical properties of the resulting compounds are shown in Table 1.

pound (5) and compound (10), in the amount indicated in Table 2, were each aded to a photographic emulsion containing 75 grams of gelatin and grams of silver bromide per kilogram of the emulsion. Specimens were prepared by uniformly applying the resulting mixture to a cellulose triacetate film based to an extent such that the thickness of the emulsion layer after drying was 10,11, and thereafter drying the resulting film. One group of the spec imens was aged at room temperature for three days, another group for 7 days, and still another group for 14 days. With respect to each of these specimens, the temperature at which the emulsion layer melted (melting point) was measured in a 2% aqueous solution of Na CO H O whose temperature was increased at a rate of 1 C. per minute. On the other hand, dry specimens which had been aged for two days under the accelerating conditions described in Table 2 were subjected to a dry scratch-resistivity test, and the melting point thereof Was determined under the same conditions. A needle fitted at its tip with a diamond ball having a radius of 0.05 mm. was pressed against the surface of the emulsion layer at right angles thereto, and moved in a parallel manner on the surface thereof at a rate of 5 mm. per second. The load of the needle under which injury occurred to the emulsion layer was measured, and termed the dry scratch-resisting strength. The results are shown in Table 2.

Furthermore, specimens which had been allowed to stand for 30 days at room temperature were each exposed by using an NSG-II type sensitometer, and developed for 10 minutes at 20 C., with a developer of the following composition:

Water to make, 1 liter.

TAB LE 1 Com- Beerystal- 0 (percent) 11 (percent) Propound Meltlng point lization Yield Dihydroxy compound used eedure No. C.) solvent (percent) Found Calculated Found Calculated 1,2-propanediol (1) 100-1015 Acetone 56 44. 96 44. 78 7. 72 7. 46' 2,3-butanediol. A (3) Wax 70 48. 28 48. 7. 85 8. l1 2,3-pentanedrol. A (4) Syrupy hqu 65 51. 38 51.85 8. 42 8. 64 1,2-0ctanediol- A. (5) 6-97 Ethanol- 68 58. 70 58. 82 10. 01 9. 1,2-dodecanediol B (6) 104-104 5 Acetone. 62 64. 38 64. 62 10. 71 10. 77 3-n-butoxy-1,2-propanediol A (8) syrupy liq id- 65 52.15 52. 38 8.91 8. 73 3-n-dodecyloxy-1,2-propanediol A (9) 80-82 Acetone 33 63. 8O 64. 15 10.81 10. 69 2-phenyl-1 ,2-ethanedio] B (10) 146.5. Ethanol 47 61. 12 61. 22 5. 6. 12 3-phenoxy-1,2-propanediol A (11) -125 5 Acetone. 57 58. 40 58.41 6. 13 6. 19 Cateehol A (12) 136-136 Water--- 44 57.03 57. 14 4. 68 4. 76 4-tert.-butyl catecho] B (13) 114116 Benzene 51 64. 27 64. 29 7. 38 7. 14

Elemental analysis values EXAMPLE 4 After fixing and rinsing in water, the photographic properties of the specimens were measured. The results are shown in Table 3.

It will be appreciated from the results shown in Table 2 that specimen Nos. 4 to 7, containing the compounds of the present invention, exhibited a more rapid hardening and a higher resistance to injury in a dry condition than specimen No. 1 containing no such compound and specimen Nos. 2 and 3 containing the known analogous compound. Furthermore, specimen Nos. 4 to 7 hardly gave adverse elfects to the photographic properties as shown in The known compound 2,'3-dihydroxy-1,4-dioxane, com- 7 Table 3.

TABLE 2 Dry scratchresisting Melting point C.) strength s) Amount. Room temperature Speeimen added Accelerating conditions No. Compound as hardener (moi/kg.) 3 days 7 days 14 days (50 0., 80% RH, 2 days) 1 None (control) 35 35 35 36 25 2,3-dihydroxy-1,4-di0xane 10- 39 45 50 57 25 x10- 41 49 59 70 25 10- 45 56 s 59 90 s 55 68 70 71 90 10- 47 60 61 63 so 3 1o- 58 75 75 76 80 TABLE 3 1r having a total number of from 7 to 18 carbon atoms; and R1 f a Z represents carbon-to-carbon chain of 4 carbon atoms Specimen f f i? Gamma Fog to form a non-substituted or mono-substituted aromatic m0 2 23 010 carbon ring of 6 carbon atoms, the substituent on said 95 ring belng alkyl of from 1 to 5 carbon atoms. 91 1. 9e 0. 0s 2. The compound of Claim 1 wherein monohaloalkyl 96 2.05 0.08 h 1 h l 94 L98 Q08 s mono a omet y as 2.10 0.08 3. The d1hydroxy1,4-dioxane compound of Claim 1: 90 2.05 0.07

EXAMPLE 5 CH-OH CH OH-OH To seven separate photographic emulsions, each con- 4 taining 75 grams of gelatin and 62 grams of silver iodoa bromide, were added various hardener compounds as The Y y-L po of Claim 12 shown in Table 4 below in the amounts shown in Table O 4. Each emulsion was applied separately to a subbed V H2O CH-OH cellulose triacetate film in such an amount as to provide a dry coating film thickness of 10 microns and then dried CEPOH to form specimens, the melting points and dry scratch- 01GB; 0 resisting strength were measured as described above. In 5 The dih drox 1 4 diox ane com ound of Claim 1: addition, the wet scratch-resisting strength" of the speciy y i I p mens subjected to the accelerated conditions was determined by soaking the specimens in a 2% aqueou solu- CH CHLOE tion of NaQCO -H O and then performing the same opl i CH (DH-OH erations as employed in measuring the dry scratch-resisting strength. The results are shown in Table 4. CH3 0 TABLE 4 Scrateh'resisting Melting point C.) strength (grams) Room temperature Dry Wot Specimen Amount No. Compound hardener (mole/kg.) 3 days 7 days 14 days Accelerated drying conditions 0 35 35 35 35 25 13 2x10- 39 25 2x10- 45 55 64 68 27 2X10-3 42 54 62 65 45 4x10- 55 69 73 75 50 2 10 42 59 66 68 60 120 4 10 55 70 74 77 60 What is claimed is:

1. A dihydroxy-l,4-dioxane compound represented by the following formuia:

O H C OH A I O OH wherein A represents 6. The dihydroxy-lA-didxane compound of Claim 1:

7. The dihydroxy-1,4-dioxane compound of Claim 1:

H 20 CHOH /CH 011 011 onnonnwom' o 8. The dihydroxy-lA-dio rane compound of Claim 1:

9 10 9. The dihydroxy-1,4-dioxane compound of Claim 1: 14. The dihydroxy-lA-dioxane compound of Claim 1:

1120 \CHOH CH H H-OH CH 011-011 \0/ CHa(CH2)14-CH2 O h -1,4-d l 10. The dihydroxy-lA-dioxanc compound of Claim 1: 15 The d1 ydroxy loxane compound of C mm 1 0 CH3 OH-OH H2O (EH-OH CH H OH /0E /CH-0H (EH omonmonho-om o 3 11. 'Ihe dihydroxy-l,4-dioxane compound of Claim 1: References Cited UNITED STATES PATENTS 2,361,456 10/1944 Chitwood 260-3406 OH 5 OTHER REFERENCES 0 Head: Chemical Abstracts, vol. 50, 1956, col. 1822g.

T11e dihYdIOXY-IA'diOXaIIe compound of Claim 11 2O Horton et 3.1.: Chemical Abstracts, vol. 59, 1963, cols.

346611-3467!)- Head: Chem1cal Abstracts, vol. 55, 1961, col. 9425f.

A} Jeffreys et a1.: Chemical Abstracts, vol. 71, 1969, G g co1.66038r.

13. The dihydroxy-1,4-dioxane compound of Claim 1: DONALD DAUS Primary Examiner J. H. TURNIPSEED, Assistant Examiner H2O US. 01. X.R.

96-111; 117-34; 260340.6 @o-cH z o 

1. A DIHYDROXY-1,4-DIOXANE COMPOUND REPRESENTED BY THE FOLLOWING FORMULA: 